Relatively scant work was related to polynaphthalene (PN) and its derivatives because of the unique nonlinear optical properties which make PN and its derivatives owning potential applications in various domains. According to relevant studies, the pursuit for the synthesis of high quality PN films is a great challenge for the applications of PN. To achieve high quality polymer films, three bridged naphthalene derivatives were designed, and finally two crosslinked PN exhibiting space network were electrosynthesized, respectively, by direct anodic oxidation from 1,6-bis(naphthalen-2-yloxy)hexane and 1,4-bis((naphthalen-2-yloxy)methyl)benzene in mixed electrolyte of dichloromethane containing boron trifluoride diethyl etherate. Furthermore, as-formed conducting films were characterized by cyclic voltammetry, spectroscopic analysis, thermal analysis, and scanning electron microscopy. And the series of characterizations indicated that films hold high stability and good blue-light-emitting property. Meanwhile, these polymer films were smooth, shiny, and flexible easily being processed into various shapes by conventional mechanical methods. Consequently, these high quality PN films will facilitate their potential applications as blue-light-emitting materials in organic light-emitting diode. Because di(naphthalen-2-yl) terephthalate was difficult to electropolymerize, the effects of bridged spacers to polymerization were also discussed. (c) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012